Multiblock copolymers of PPC with oligomeric PBS: with low brittle–toughness transition temperature

In order to decrease the brittle–toughness transition temperature and increase the mechanical strength of poly(propylene carbonate) (PPC), a series of multiblock copolymers of poly(propylene carbonate)-multiblock-poly(butylene succinate) (PPC-mb-PBS) are designed and synthesized. 1H-NMR, DOSY and GPC results demonstrate the successful synthesis of PPC-mb-PBSs with designed multiblock sequence. The thermal, crystalline and mechanical properties of these PPC-mb-PBSs are evaluated by DSC, TGA, POM, tensile and tearing testing. Experiment results demonstrate that crystallinity, thermal and mechanical properties of PPC-mb-PBSs can be readily modulated by changing the composition and block length of PPC and PBS moieties. It is found that all the prepared PPC-mb-PBSs are semi-crystalline polymers with a melting temperature at 93–109 °C and a Tg at around −40 °C. Both crystallization rate and crystallinity of the multiblock copolymers increase with increasing both PBS content and PBS block length. As a consequent, the tensile strength increases with increasing PBS/PPC block ratios at room and lower temperatures. In conclusion, the amorphous PBS phase in the block copolymers acts as soft segment, endowing PPC-mb-PBS copolymers with much better flexibility than PPC at low temperature of 273 K when PPC segments are frozen.

[1]  Charlotte K. Williams,et al.  Chemoselective Polymerizations from Mixtures of Epoxide, Lactone, Anhydride, and Carbon Dioxide. , 2016, Journal of the American Chemical Society.

[2]  Charlotte K. Williams,et al.  Selective polymerization catalysis: controlling the metal chain end group to prepare block copolyesters. , 2015, Journal of the American Chemical Society.

[3]  Yu-Zhong Wang,et al.  Synthesis, characterization and isothermal crystallization behavior of poly(butylene succinate)-b-poly(diethylene glycol succinate) multiblock copolymers , 2015 .

[4]  M. Xiao,et al.  Thermal degradation of poly(lactide-co-propylene carbonate) measured by TG/FTIR and Py-GC/MS , 2015 .

[5]  Linbo Wu,et al.  Poly(l-lactic acid)-block-poly(butylene succinate-co-butylene adipate) Multiblock Copolymers: From Synthesis to Thermo-Mechanical Properties , 2014 .

[6]  D. Darensbourg,et al.  A one-pot synthesis of a triblock copolymer from propylene oxide/carbon dioxide and lactide: intermediacy of polyol initiators. , 2013, Angewandte Chemie.

[7]  H. Frey,et al.  Propargyl-functional aliphatic polycarbonate obtained from carbon dioxide and glycidyl propargyl ether. , 2013, Macromolecular rapid communications.

[8]  M. Xiao,et al.  Orientation Microstructure and Properties of Poly(propylene carbonate)/Poly(butylene succinate) Blend Films , 2013 .

[9]  D. Darensbourg,et al.  Tandem metal-coordination copolymerization and organocatalytic ring-opening polymerization via water to synthesize diblock copolymers of styrene oxide/CO2 and lactide. , 2012, Journal of the American Chemical Society.

[10]  Jacek Gregorowicz,et al.  Aliphatic Hyperbranched Polycarbonates: Synthesis, Characterization, and Solubility in Supercritical Carbon Dioxide , 2012 .

[11]  D. Darensbourg,et al.  Depolymerization of Polycarbonates Derived from Carbon Dioxide and Epoxides to Provide Cyclic Carbonates. A Kinetic Study , 2012 .

[12]  J. Coudane,et al.  Diffusion ordered spectroscopy (DOSY) as a powerful tool for amphiphilic block copolymer characterization and for critical micelle concentration (CMC) determination , 2012 .

[13]  M. Picquet,et al.  Organo-catalyzed synthesis of aliphatic polycarbonates in solvent-free conditions , 2012 .

[14]  U. Sivagnanam,et al.  Development and Characterization of Electropsun Poly(propylene carbonate) Ultrathin Fibers as Tissue Engineering Scaffolds , 2012 .

[15]  Xian‐Zheng Zhang,et al.  Construction of functional aliphatic polycarbonates for biomedical applications , 2012 .

[16]  D. Darensbourg,et al.  Cobalt catalysts for the coupling of CO2 and epoxides to provide polycarbonates and cyclic carbonates. , 2012, Chemical Society reviews.

[17]  Alex Tullo,et al.  TRONOX WILL MERGE WITH ORE SUPPLIER: INORGANICS: Company says Exxaro unit will enable it to expand to meet demand , 2011 .

[18]  Jun Xu,et al.  Poly(butylene succinate) and its copolymers: Research, development and industrialization , 2010, Biotechnology journal.

[19]  J. Varghese,et al.  Thermal and weathering degradation of poly(propylene carbonate) , 2010 .

[20]  B. Lee,et al.  Terpolymerizations of CO2, Propylene Oxide, and Various Epoxides Using a Cobalt(III) Complex of Salen-Type Ligand Tethered by Four Quaternary Ammonium Salts , 2010 .

[21]  D. Darensbourg,et al.  Highly Selective and Reactive (salan)CrCl Catalyst for the Copolymerization and Block Copolymerization of Epoxides with Carbon Dioxide , 2009 .

[22]  Ryan C. Jeske,et al.  Pre-rate-determining selectivity in the terpolymerization of epoxides, cyclic anhydrides, and CO2: a one-step route to diblock copolymers. , 2008, Angewandte Chemie.

[23]  M. Xiao,et al.  Thermally stable aliphatic polycarbonate containing bulky carbazole pendants , 2008 .

[24]  M. Xiao,et al.  Thermally stable poly(propylene carbonate) synthesized by copolymerizing with bulky naphthalene containing monomer , 2008 .

[25]  M. Xiao,et al.  Miscibility and properties of completely biodegradable blends of poly(propylene carbonate) and poly(butylene succinate) , 2008 .

[26]  G. Luinstra Poly(Propylene Carbonate), Old Copolymers of Propylene Oxide and Carbon Dioxide with New Interests: Catalysis and Material Properties , 2008 .

[27]  J. Jung,et al.  Acid- and base-catalyzed hydrolyses of aliphatic polycarbonates and polyesters , 2006 .

[28]  You Han Bae,et al.  Thermogelling aqueous solutions of alternating multiblock copolymers of poly(L-lactic acid) and poly(ethylene glycol). , 2006, Biomacromolecules.

[29]  Dae-Won Park,et al.  Aliphatic polycarbonate synthesis by copolymerization of carbon dioxide with epoxides over double metal cyanide catalysts prepared by using ZnX2 (X = F, Cl, Br, I) , 2006 .

[30]  Rong Zhang,et al.  Design of highly active binary catalyst systems for CO2/epoxide copolymerization: polymer selectivity, enantioselectivity, and stereochemistry control. , 2006, Journal of the American Chemical Society.

[31]  Haiming Li,et al.  Synthesis and characterization of biodegradable poly(3-hydroxybutyrate) and poly(ethylene glycol) multiblock copolymers , 2005 .

[32]  Dimitrios N. Bikiaris,et al.  Thermal degradation mechanism of poly(ethylene succinate) and poly(butylene succinate) : Comparative study , 2005 .

[33]  Y. Meng,et al.  Kinetic analysis of thermal decomposition of poly(propylene carbonate) , 2005 .

[34]  D. Cohn,et al.  Designing biodegradable multiblock PCL/PLA thermoplastic elastomers. , 2005, Biomaterials.

[35]  David R. Moore,et al.  Discrete metal-based catalysts for the copolymerization of CO2 and epoxides: discovery, reactivity, optimization, and mechanism. , 2004, Angewandte Chemie.

[36]  Young Ha Kim,et al.  Synthesis and Characterization of Poly(l-lactide)−Poly(ε-caprolactone) Multiblock Copolymers , 2003 .

[37]  S. Ray,et al.  Structure-Property Relationship in Biodegradable Poly(butylene succinate)/Layered Silicate Nanocomposites , 2003 .

[38]  David R. Moore,et al.  High-activity, single-site catalysts for the alternating copolymerization of CO2 and propylene oxide. , 2002, Journal of the American Chemical Society.

[39]  Q. Zhu,et al.  Effects of the structure and morphology of zinc glutarate on the fixation of carbon dioxide into polymer , 2002 .

[40]  Min Zhang,et al.  Degradation and Stabilization of Poly(propylene carbonate) , 2002 .

[41]  Y. Bae,et al.  Biodegradable amphiphilic multiblock copolymers and their implications for biomedical applications. , 2000, Journal of controlled release : official journal of the Controlled Release Society.

[42]  R. Gross,et al.  Aliphatic Polycarbonates with Controlled Quantities of d-Xylofuranose in the Main Chain , 1999 .

[43]  F. Ignatious,et al.  Synthesis and characterization of block copolymers containing rigid liquid crystalline and flexible butylene terephthalate segments , 1994 .

[44]  A. Ayas,et al.  Preparation of ABCBA-type block copolymers by use of macro-initiators containing peroxy and azo groups , 1989 .

[45]  M. Xiao,et al.  Biodegradable poly(propylene carbonate)/layered double hydroxide composite films with enhanced gas barrier and mechanical properties , 2015, Chinese Journal of Polymer Science.

[46]  S. Tjong,et al.  Thermal decomposition characteristics of poly(propylene carbonate) using TG/IR and PY-GC/MS techniques , 2003 .

[47]  R. Zhuo,et al.  Synthesis and characterization of novel aliphatic polycarbonates , 2002 .